Research ArticleKinetic Study of the Adsorption of Polyphenols from Olive MillWastewater onto Natural Clay Ghassoul

Safae Allaoui 1 Mohammed Naciri Bennani1 Hamid Ziyat 1 Omar Qabaqous1

Najib Tijani2 and Najim Ittobane3

1Laboratory of Chemistry-Biology Applied to the Environment Research Team ldquoApplied Materials and CatalysisrdquoChemistry Department Faculty of Sciences Moulay-Ismaıl University BP 11201-Zitoune Meknes 50000 Morocco2Research Team ldquoMembrane Materials and Separation Processesrdquo Chemistry Department Faculty of ScienceMoulay-Ismaıl University BP 11201-Zitoune Meknes 50000 Morocco3Research Team ldquoBiomolecular and Macromolecular Chemistryrdquo Chemistry Department Faculty of ScienceMoulay-Ismaıl University BP 11201-Zitoune Meknes 50000 Morocco

Correspondence should be addressed to Safae Allaoui allaouisafaegmailcom

Received 7 December 2019 Accepted 11 March 2020 Published 25 April 2020

Guest Editor Lisa Yu

Copyright copy 2020 Safae Allaoui et al )is is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

)e aim of this study is based on natural clay as an adsorbent in the elimination of polyphenols from olive mill wastewater(OMW) )is clay was analyzed using XRD SEMEDX FTIR surface area measurement (BETmethod) thermal analysis (TGADTA) and X-ray fluorescence (XRF) and then used in adsorption experiments )e results reveal that the best quantity ofadsorption of polyphenols is 161mgg at the temperature of 25degC but they decrease at 35degC and 45degC A great agreement withpseudo-second-order and Freundlich model is represented by kinetic and isotherms models and several parameters such as ΔG0ΔS0 and ΔH0 were determined using the thermodynamic function relationship

1 Introduction

)eolivemill wastewaters (OMWs) from two-phase extractionsystems are deemed to be one of the main environmentalproblems in region Fes-Meknes Morocco (Figure 1) due topresence of toxic elements such as polyphenols In 2016Morocco generated 4000 to 5000 tonnes of OMW diverse inthe rivers [1] because we used greater quantities of water whichgenerate large volumes of the latter [2]

OMW is an environmental threat and it became aproblem that needs to be solved by the olive industry [3])ecomposition of OMW may vary significantly depending onseveral factors climate conditions olive storage periodextraction process and period of production [4]

Many physicochemical and biological techniques havebeen developed to treat OMW )ese methods includecoagulationflocculation [5 6] oxidation ozonation [7] andmembrane filtration [3 7 8] Despite the availability of theprocesses above the adsorption method is most extensivelyemployed for treatments of the OMW

For instance Curi and Velioglu [9] and Azzam [10]utilized activated charcoal and natural clay for adsorption ofhydroxytyrosol and other phenolic mixes from OMW

)e goal of this research is the elimination of OMWpolyphenols onto a low-cost clay called ghassoul and thecharacterization of this material For this purpose thequantity of polyphenols retained has been determined at theequilibrium )e isotherms to Langmuir and Freundlichmodels have been described Moreover the kinetic of ad-sorption has been analyzed uses pseudo-first-order (PFO)pseudo-second-order (PSO) and WeberndashMorris intra-particle diffusion (IPD) models

2 Materials and Methods

21 Material )e material used is the commercial clay la-belled ldquoGhassoul Chorafa Al Akhdarrdquo without any furthertreatment native from a site called ldquoKsabirdquo in the Province ofMissour East of Middle Atlas (Fez-Morocco) )e particlesof size lt63 nm are crushed and dried during 24 hours at 80degC

HindawiJournal of ChemistryVolume 2020 Article ID 7293189 11 pageshttpsdoiorg10115520207293189

in the steam room )e prepared product was called Gh-Breferring to unprocessed ghassoul

22 Olive Mill Wastewater and Pretreatment )e originolive from Taza (Morocco) and the OMW was obtainedfrom a two-phase discontinuous extraction factory in theFes-Meknes region (Morocco) on 20 November 2018 )egathered OMW was kept in separate plastic containers untiluse and then treated under nitrogen stream to removedissolved oxygen to protect polyphenols )e sample ob-tained was then filtered and conserved to prepare a stocksolution for kinetic study

23 Physical Chemical and Mineralogical Characterisation)e Gh-B was characterized by physicochemical techniques(XRD FTIR BET DTATGA SEM EDX and XRF)

For X-ray diffraction analysis the Philips PW 1800instrument has been utilized )e quickening voltage was40 kV the current was 20mA and the copper Kα radiationwas λ 15418 A )e spectra of the different samples wereregistered in an interval of 2θ (5degndash70deg) with an accurateaddition of 004deg

FTIR investigation was directed by using FourierTransform Infrared Spectrometer (JASCO 4000) out fittedin with a detector (TGS) and a ceramic source isolated by anoptical framework utilizing an interferometer of MichelsonFTIR spectra are extended somewhere in the range of 4000and 400 cmminus1

)e Micromeritics ASAP 2010 Gas Sorption System wasused to measure the surface area and both methods of BETand BJH were utilized for determination of the specificsurface and the pore size

)ermogravimetric (TGA-DTA) investigation wascompleted by using Shimadzu TA-60 type contraptionworking under air with a direct warming rate of 10degCmiddotminminus1

from surrounding temperature to 600degC)e technique of SEM-EDX was utilized to determine

the morphology and elemental composition of the Gh-B)e Gh-B dried at 105degC was analyzed by using X-ray

fluorescence Philips PW 1666 type to determine thechemical composition such as P2O5 Al2O3 MgO Fe2O3BaO and SiO2

24KineticofAdsorptionofPolyphenols fromOMWontoGh-BAdsorption tests were done in black bottles to avoid thedegradation of polyphenols 50mg of Gh-B with 50mL ofOMW was diluted in water (starting focus C0 30mgmiddotLminus1))e blends were waved at temperatures of 25degC 35degC and45degC during different times (20min to 180min) After eachtime the blend is segregated by centrifugation at 3400 rpmfor 8min and the supernatant was examined for determi-nation of total polyphenols utilizing the FolinndashCiocalteu [11]technique and analyzed by UV-Vis spectroscopy )e ab-sorbance at the wavelength of 760 nm was determined tocalculate the leftover concentration of polyphenols (CegmiddotLminus1) and amount of polyphenols adsorbed at equilibriumtime (qe in mgmiddotgminus1) was calculated utilizing the followingequation [12]

qe C0 minus Ce( 1113857 times V

m (1)

where C0 is the initial concentration of polyphenols Ce is theleftover concentration of polyphenols which are expressedby gmiddotLminus1 m (mg) is the lump of Gh-B and V (mL) is thevolume of OMW diluted

30003000

20002000

10001000

500500

200200

100100

0m0m

00 100100 200200 300300 400km400km

Figure 1 Geographical map of the origin of olive (taza) and sampling OMW (Fes) Morocco

2 Journal of Chemistry

)e adsorption isotherms were done under identicalconditions from those of the adsorption kinetic utilizing alarger concentration from 0 to 58mgmiddotLminus1 of polyphenols)e solutions were mixed for 3 hours until the equilibriumtime was attained and then centrifuged )e determinationof residual concentrations and the adsorbed amounts wasdone using (1)

25 gteoretical Background We present in this part theexpressions utilized to represent the kinetic and isotherms ofthe examined models

26 Modelling of Kinetic Studies

261 Kinetic of PFO )e kinetic model Lagergren [13] ofpseudo-first-order (PFO) is represented by the followingequation

ln qe minus qt( 1113857 ln qe minus K1t (2)

where qt is the capacity adsorbed at time t qe is the capacityadsorbed at balanced which are expressed by mgmiddotgminus1 and K1(minminus1) is the speed constant of PFO K1 and qe can bedetermined by plotting ln(qe minus qt) versus the time t

262 Kinetic of PSO )e expression of the pseudo-second-order (PSO) model [13 14] is represented by the followingequation

t

qt

1

K2 times q2e+

t

qe (3)

where K2 (gmiddotmgminus1middotminminus1) is the speed constant for the PSOand qe is the quantity of polyphenols adsorbed at the bal-anced (mgmiddotgminus1) )e slope and the y-intercept are utilized tocalculate K2 of PSO and qe

263 Model of IPD )e determination of intraparticlediffusion models is done using equation (4) (WeberndashMorrisequation) [14 15] )is model is used to determine thelimiting step in the adsorption mechanism

qt Kd times t12

+ C (4)

where Kd is the IPD constant in mgmiddotgminus1middotminminus12 and Crepresents the value of the thickness of the boundary layer)ey can both be determined from slope and the y-intercept(equation (4))

27 Adsorption of Isotherm Studies In the literature variousmodels have been published to compare experimental andtheoretical data of adsorption isotherms Freundlich andLangmuir models were utilized to describe isothermadsorption

271 Langmuir Model )e nonlinear shape of the Lang-muir model [14] is expressed by the following equation

qe

qmax

KL times Ce( 1113857

1 + KL times Ce( 1113857 (5)

where KL is the Langmuir constant (Lmiddotmgminus1) Ce is theequilibrium polyphenol concentration (mgmiddotLminus1) qe is theadsorption capacity of polyphenols at equilibrium (mgmiddotgminus1)and qm is the maximum adsorption amount for a monolayer(mgmiddotgminus1) Another parameter labelled separation factor (RL)[16 17] is expressed in the following equation

RL 1

1 + KL times C0 (6)

where C0 is the initial concentration of the adsorbate(mgmiddotLminus1) RL is the factor of separation which allows to checkwhether the isotherm is favorable or not provided that if thevalue of RL is between 0 and 1 it confirms the validity of theLangmuir model when RL is close to 1 or 0 it signifies thatthe isotherms are linear and irreversible respectively and ifRL is upper to 1 it indicate that isotherm is unfavourable[16 17]

272 Freundlich Model )e nonlinear type of theFreundlich model [15 18] can be calculated by the followingequation

qe KF times C1ne (7)

where qe is the equilibrium polyphenol concentration on theghassoul Ce is the equilibrium polyphenol concentration ofsolution KF is the Freundlich constant and n is the ad-sorption intensity characterizing the affinity of the pollutantfor the adsorbent when n is close to 1 it signifies a chemicaladsorption process and when n is greater than 1 it indicatesa physical adsorption mechanism

273 gtermodynamic Parameters of Adsorption )e en-thalpy (ΔH0) free energy (ΔG0) and entropy (ΔS0) ther-modynamic parameters are calculated by the followingrelations [19]

ΔG0 minusRT ln(K)

lnK ΔS0

R+ΔH0

RT

(8)

where KC is the equilibrium constant defined as follows

KC Cads

C0

Ce minus C0( 1113857

Ce (9)

in which Cads is the adsorbed concentration (gL) and C0 isthe initial concentration of polyphenols in OMW (gL)

3 Results and Discussion

31 Physicochemical Characterization of Gh-B

311 XRD Study XRD analyses (Figure 2) showed that Gh-B consists of three phases of clay

Journal of Chemistry 3

(i) Stevensite (S) observed at the 2θ 570deg 1161deg1933deg 2943deg 3340deg and 4484deg

(ii) Dolomite (D) observed at the 2θ 3083deg 3458deg4103deg and 3522deg

(iii) Quartz (Q) observed at the 2θ 2073deg 2652deg and5370deg

One also notices the presence of free silica in the shape ofquartz and dolomite in very small amount On the contrarythe stevensite and magnesia poles of the smectites series aredominant in the Gh-B )ese outcomes are congruent withthose obtained in the literature [19ndash21]

312 XRF Analysis XRF was carried out to identify thechemical composition of the minerals present in the Gh-B

)e information given in Table 1 demonstrates that themagnesium and silica oxides are available in a large quantitythe presence of alumina (Al2O3) is very important and otherelements are present in trace quantity )ese results are inagreement with the XRD results and those cited by otherauthors such as Elass et al and Ajbary et al [20 21]

313 FTIR Analysis )e spectra of natural clay (Gh-B)demonstrate a large absorption band at 3437 cmminus1 corre-sponding to the OH-stretching vibration of the watermolecules )e bending mode of the interlayer andoradsorbed water appears around 1641 cmminus1 )e stretchingvibrations anti-symmetric C-O around 1450 cmminus1 show thepresence of the carbonate anions (υas (CO3

minus2)) inside wallsBoth vibrations of (υs (CO3

minus2)) and Al2O3 groups are

10 20 302θ (deg)

40 50 60

0

500

1000

1500

2000

2500

D S

QD

D

S

D

S

Q

Q

S

S

Inte

nsity

(au

)

S StevensiteD DolomiteQ Quartz

Figure 2 X-ray diffraction patterns of Gh-B

Table 1 Chemical composition of Gh-B

Name of compound P2O5 Fe2O3 SiO2 BaO MgO MO Al2O3

of oxide 00325 1544 42965 00314 13532 0290 2514Element in S Ca F Sn As Cu Zn Pb Ag() 4303 6770 0940 ltLD ltLD 0009 0006 0006 ltLDLD limit of detection

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumbers (cmndash1)

Gh-B

1021

880684

463

14501641

3435

Figure 3 FTIR spectra of Gh-B

4 Journal of Chemistry

observed at 880 cmminus1 )e bands which appear around 1021684 and 463 cmminus1 are attributed to the vibrations of the SiO2group (Figure 3)

314 SEMEDX and BET Analysis SEMmicrograph of Gh-B (Figure 4) shows that the morphology of the Gh-B is closeto hectorite and the particles from different sizes have theappearance of sheets which oriented parallel to each other asindicated by Caillere and Henin [22]

)e chemical elements contained in natural clay (Gh-B) were detected by EDX analysis and the results showthat Gh-B has a higher percentage of silica (Table 2)mainly due to the presence of majority of quartz followedby magnesia )ese results are in agreement with XRD andXRF analysis

Table 2 gives the chemical elements and their masspercentages determined by the EDX analysis

)e nitrogen adsorptiondesorption isotherms of Gh-Bshow that according the IUPAC classification isothermobtained is type IV characteristic of solid mesoporous withonset the hysteresis of H3 type After calculating using theBET method the specific surface is 296m2g

)e pore size distribution is determined from desorptionisotherm by the BJH method shown in Figure 5 )is lattershows that the pore diameter is in the order of 73 A and thusconfirms the mesoporosity of the structure of the Gh-B

315 gtermal Analysis (DTATGA) TGADTA thermo-gram (Figure 6) shows that the breakdown of Gh-B is doneon three exothermic steps and one endothermic step

315

280

245

210

175

140

105

70

35

000 13 26

Lsec 300 0 Cnts 0000keV Det octane plus det39 52 65 78 91 104 117 130

Figure 4 SEM images and EDX analysis of Gh-B

Table 2 Chemical elements of Gh-B and their

Element O Fe Mg Al Si S K Ca masses 479 4 138 1 238 07 06 82

Journal of Chemistry 5

(i) First degradation step with loss of mass on theorder of 12 due to the removal of water moleculesinfirm bound or adsorbed on external faces of thecrystals )is step manifests itself by two distinctendothermic peaks on curve ATD at two tem-peratures 7070degC and 12895degC respectively

(ii) Second loss of almost 895 mass at 67937degC(ATD) which is manifested by wide and asym-metric peak corresponding to decomposition of theearly mixed carbon of magnesia and the calcium

(iii) Exothermic pic around 528degC corresponding toallotropic transformation of the stevensite inenstatite

)at transformation of stevensite in enstatite is repre-sented by the following equation

2Mg3Si4O10(OH)2 middot nH2O⟶ 3 MgSiO3 + MgO( 1113857 + 5SiO2

+ 2(n + 1)H2O

(10)

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

0 200 400 600 800 1000 1200 1400ndash0002

00000002000400060008001000120014

dVd

D (c

m3 g

A)

Pore diameter (Adeg)

D = 72812A

Vol

ume a

dsor

bed

(cm

3 g S

TP)

Relative pressure (PP0)

Adsorption Desorption

Figure 5 N2 adsorptiondesorption isotherms of Gh-B

0 100 200 300 400 500 600 700 80050

55

60

65

70

75

80

85

90

95

100

Temperature (degC)

Wei

ght (

)

12412615mg

89521886mg

11925degC

7070degC

52848degC

67937degC

ATGATD

ndash0213

ndash0142

ndash0071

0000

0071

0142

0213

Tem

pera

ture

diff

eren

ce (deg

Cm

g)

Figure 6 DTA and TGA plots of Gh-B

6 Journal of Chemistry

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

)e adsorption isotherms were done under identicalconditions from those of the adsorption kinetic utilizing alarger concentration from 0 to 58mgmiddotLminus1 of polyphenols)e solutions were mixed for 3 hours until the equilibriumtime was attained and then centrifuged )e determinationof residual concentrations and the adsorbed amounts wasdone using (1)

25 gteoretical Background We present in this part theexpressions utilized to represent the kinetic and isotherms ofthe examined models

26 Modelling of Kinetic Studies

261 Kinetic of PFO )e kinetic model Lagergren [13] ofpseudo-first-order (PFO) is represented by the followingequation

ln qe minus qt( 1113857 ln qe minus K1t (2)

where qt is the capacity adsorbed at time t qe is the capacityadsorbed at balanced which are expressed by mgmiddotgminus1 and K1(minminus1) is the speed constant of PFO K1 and qe can bedetermined by plotting ln(qe minus qt) versus the time t

262 Kinetic of PSO )e expression of the pseudo-second-order (PSO) model [13 14] is represented by the followingequation

t

qt

1

K2 times q2e+

t

qe (3)

where K2 (gmiddotmgminus1middotminminus1) is the speed constant for the PSOand qe is the quantity of polyphenols adsorbed at the bal-anced (mgmiddotgminus1) )e slope and the y-intercept are utilized tocalculate K2 of PSO and qe

263 Model of IPD )e determination of intraparticlediffusion models is done using equation (4) (WeberndashMorrisequation) [14 15] )is model is used to determine thelimiting step in the adsorption mechanism

qt Kd times t12

+ C (4)

where Kd is the IPD constant in mgmiddotgminus1middotminminus12 and Crepresents the value of the thickness of the boundary layer)ey can both be determined from slope and the y-intercept(equation (4))

27 Adsorption of Isotherm Studies In the literature variousmodels have been published to compare experimental andtheoretical data of adsorption isotherms Freundlich andLangmuir models were utilized to describe isothermadsorption

271 Langmuir Model )e nonlinear shape of the Lang-muir model [14] is expressed by the following equation

qe

qmax

KL times Ce( 1113857

1 + KL times Ce( 1113857 (5)

where KL is the Langmuir constant (Lmiddotmgminus1) Ce is theequilibrium polyphenol concentration (mgmiddotLminus1) qe is theadsorption capacity of polyphenols at equilibrium (mgmiddotgminus1)and qm is the maximum adsorption amount for a monolayer(mgmiddotgminus1) Another parameter labelled separation factor (RL)[16 17] is expressed in the following equation

RL 1

1 + KL times C0 (6)

where C0 is the initial concentration of the adsorbate(mgmiddotLminus1) RL is the factor of separation which allows to checkwhether the isotherm is favorable or not provided that if thevalue of RL is between 0 and 1 it confirms the validity of theLangmuir model when RL is close to 1 or 0 it signifies thatthe isotherms are linear and irreversible respectively and ifRL is upper to 1 it indicate that isotherm is unfavourable[16 17]

272 Freundlich Model )e nonlinear type of theFreundlich model [15 18] can be calculated by the followingequation

qe KF times C1ne (7)

where qe is the equilibrium polyphenol concentration on theghassoul Ce is the equilibrium polyphenol concentration ofsolution KF is the Freundlich constant and n is the ad-sorption intensity characterizing the affinity of the pollutantfor the adsorbent when n is close to 1 it signifies a chemicaladsorption process and when n is greater than 1 it indicatesa physical adsorption mechanism

273 gtermodynamic Parameters of Adsorption )e en-thalpy (ΔH0) free energy (ΔG0) and entropy (ΔS0) ther-modynamic parameters are calculated by the followingrelations [19]

ΔG0 minusRT ln(K)

lnK ΔS0

R+ΔH0

RT

(8)

where KC is the equilibrium constant defined as follows

KC Cads

C0

Ce minus C0( 1113857

Ce (9)

in which Cads is the adsorbed concentration (gL) and C0 isthe initial concentration of polyphenols in OMW (gL)

3 Results and Discussion

31 Physicochemical Characterization of Gh-B

311 XRD Study XRD analyses (Figure 2) showed that Gh-B consists of three phases of clay

Journal of Chemistry 3

(i) Stevensite (S) observed at the 2θ 570deg 1161deg1933deg 2943deg 3340deg and 4484deg

(ii) Dolomite (D) observed at the 2θ 3083deg 3458deg4103deg and 3522deg

(iii) Quartz (Q) observed at the 2θ 2073deg 2652deg and5370deg

One also notices the presence of free silica in the shape ofquartz and dolomite in very small amount On the contrarythe stevensite and magnesia poles of the smectites series aredominant in the Gh-B )ese outcomes are congruent withthose obtained in the literature [19ndash21]

312 XRF Analysis XRF was carried out to identify thechemical composition of the minerals present in the Gh-B

)e information given in Table 1 demonstrates that themagnesium and silica oxides are available in a large quantitythe presence of alumina (Al2O3) is very important and otherelements are present in trace quantity )ese results are inagreement with the XRD results and those cited by otherauthors such as Elass et al and Ajbary et al [20 21]

313 FTIR Analysis )e spectra of natural clay (Gh-B)demonstrate a large absorption band at 3437 cmminus1 corre-sponding to the OH-stretching vibration of the watermolecules )e bending mode of the interlayer andoradsorbed water appears around 1641 cmminus1 )e stretchingvibrations anti-symmetric C-O around 1450 cmminus1 show thepresence of the carbonate anions (υas (CO3

minus2)) inside wallsBoth vibrations of (υs (CO3

minus2)) and Al2O3 groups are

10 20 302θ (deg)

40 50 60

0

500

1000

1500

2000

2500

D S

QD

D

S

D

S

Q

Q

S

S

Inte

nsity

(au

)

S StevensiteD DolomiteQ Quartz

Figure 2 X-ray diffraction patterns of Gh-B

Table 1 Chemical composition of Gh-B

Name of compound P2O5 Fe2O3 SiO2 BaO MgO MO Al2O3

of oxide 00325 1544 42965 00314 13532 0290 2514Element in S Ca F Sn As Cu Zn Pb Ag() 4303 6770 0940 ltLD ltLD 0009 0006 0006 ltLDLD limit of detection

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumbers (cmndash1)

Gh-B

1021

880684

463

14501641

3435

Figure 3 FTIR spectra of Gh-B

4 Journal of Chemistry

observed at 880 cmminus1 )e bands which appear around 1021684 and 463 cmminus1 are attributed to the vibrations of the SiO2group (Figure 3)

314 SEMEDX and BET Analysis SEMmicrograph of Gh-B (Figure 4) shows that the morphology of the Gh-B is closeto hectorite and the particles from different sizes have theappearance of sheets which oriented parallel to each other asindicated by Caillere and Henin [22]

)e chemical elements contained in natural clay (Gh-B) were detected by EDX analysis and the results showthat Gh-B has a higher percentage of silica (Table 2)mainly due to the presence of majority of quartz followedby magnesia )ese results are in agreement with XRD andXRF analysis

Table 2 gives the chemical elements and their masspercentages determined by the EDX analysis

)e nitrogen adsorptiondesorption isotherms of Gh-Bshow that according the IUPAC classification isothermobtained is type IV characteristic of solid mesoporous withonset the hysteresis of H3 type After calculating using theBET method the specific surface is 296m2g

)e pore size distribution is determined from desorptionisotherm by the BJH method shown in Figure 5 )is lattershows that the pore diameter is in the order of 73 A and thusconfirms the mesoporosity of the structure of the Gh-B

315 gtermal Analysis (DTATGA) TGADTA thermo-gram (Figure 6) shows that the breakdown of Gh-B is doneon three exothermic steps and one endothermic step

315

280

245

210

175

140

105

70

35

000 13 26

Lsec 300 0 Cnts 0000keV Det octane plus det39 52 65 78 91 104 117 130

Figure 4 SEM images and EDX analysis of Gh-B

Table 2 Chemical elements of Gh-B and their

Element O Fe Mg Al Si S K Ca masses 479 4 138 1 238 07 06 82

Journal of Chemistry 5

(i) First degradation step with loss of mass on theorder of 12 due to the removal of water moleculesinfirm bound or adsorbed on external faces of thecrystals )is step manifests itself by two distinctendothermic peaks on curve ATD at two tem-peratures 7070degC and 12895degC respectively

(ii) Second loss of almost 895 mass at 67937degC(ATD) which is manifested by wide and asym-metric peak corresponding to decomposition of theearly mixed carbon of magnesia and the calcium

(iii) Exothermic pic around 528degC corresponding toallotropic transformation of the stevensite inenstatite

)at transformation of stevensite in enstatite is repre-sented by the following equation

2Mg3Si4O10(OH)2 middot nH2O⟶ 3 MgSiO3 + MgO( 1113857 + 5SiO2

+ 2(n + 1)H2O

(10)

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

0 200 400 600 800 1000 1200 1400ndash0002

00000002000400060008001000120014

dVd

D (c

m3 g

A)

Pore diameter (Adeg)

D = 72812A

Vol

ume a

dsor

bed

(cm

3 g S

TP)

Relative pressure (PP0)

Adsorption Desorption

Figure 5 N2 adsorptiondesorption isotherms of Gh-B

0 100 200 300 400 500 600 700 80050

55

60

65

70

75

80

85

90

95

100

Temperature (degC)

Wei

ght (

)

12412615mg

89521886mg

11925degC

7070degC

52848degC

67937degC

ATGATD

ndash0213

ndash0142

ndash0071

0000

0071

0142

0213

Tem

pera

ture

diff

eren

ce (deg

Cm

g)

Figure 6 DTA and TGA plots of Gh-B

6 Journal of Chemistry

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

(i) Stevensite (S) observed at the 2θ 570deg 1161deg1933deg 2943deg 3340deg and 4484deg

(ii) Dolomite (D) observed at the 2θ 3083deg 3458deg4103deg and 3522deg

(iii) Quartz (Q) observed at the 2θ 2073deg 2652deg and5370deg

One also notices the presence of free silica in the shape ofquartz and dolomite in very small amount On the contrarythe stevensite and magnesia poles of the smectites series aredominant in the Gh-B )ese outcomes are congruent withthose obtained in the literature [19ndash21]

312 XRF Analysis XRF was carried out to identify thechemical composition of the minerals present in the Gh-B

)e information given in Table 1 demonstrates that themagnesium and silica oxides are available in a large quantitythe presence of alumina (Al2O3) is very important and otherelements are present in trace quantity )ese results are inagreement with the XRD results and those cited by otherauthors such as Elass et al and Ajbary et al [20 21]

313 FTIR Analysis )e spectra of natural clay (Gh-B)demonstrate a large absorption band at 3437 cmminus1 corre-sponding to the OH-stretching vibration of the watermolecules )e bending mode of the interlayer andoradsorbed water appears around 1641 cmminus1 )e stretchingvibrations anti-symmetric C-O around 1450 cmminus1 show thepresence of the carbonate anions (υas (CO3

minus2)) inside wallsBoth vibrations of (υs (CO3

minus2)) and Al2O3 groups are

10 20 302θ (deg)

40 50 60

0

500

1000

1500

2000

2500

D S

QD

D

S

D

S

Q

Q

S

S

Inte

nsity

(au

)

S StevensiteD DolomiteQ Quartz

Figure 2 X-ray diffraction patterns of Gh-B

Table 1 Chemical composition of Gh-B

Name of compound P2O5 Fe2O3 SiO2 BaO MgO MO Al2O3

of oxide 00325 1544 42965 00314 13532 0290 2514Element in S Ca F Sn As Cu Zn Pb Ag() 4303 6770 0940 ltLD ltLD 0009 0006 0006 ltLDLD limit of detection

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumbers (cmndash1)

Gh-B

1021

880684

463

14501641

3435

Figure 3 FTIR spectra of Gh-B

4 Journal of Chemistry

observed at 880 cmminus1 )e bands which appear around 1021684 and 463 cmminus1 are attributed to the vibrations of the SiO2group (Figure 3)

314 SEMEDX and BET Analysis SEMmicrograph of Gh-B (Figure 4) shows that the morphology of the Gh-B is closeto hectorite and the particles from different sizes have theappearance of sheets which oriented parallel to each other asindicated by Caillere and Henin [22]

)e chemical elements contained in natural clay (Gh-B) were detected by EDX analysis and the results showthat Gh-B has a higher percentage of silica (Table 2)mainly due to the presence of majority of quartz followedby magnesia )ese results are in agreement with XRD andXRF analysis

Table 2 gives the chemical elements and their masspercentages determined by the EDX analysis

)e nitrogen adsorptiondesorption isotherms of Gh-Bshow that according the IUPAC classification isothermobtained is type IV characteristic of solid mesoporous withonset the hysteresis of H3 type After calculating using theBET method the specific surface is 296m2g

)e pore size distribution is determined from desorptionisotherm by the BJH method shown in Figure 5 )is lattershows that the pore diameter is in the order of 73 A and thusconfirms the mesoporosity of the structure of the Gh-B

315 gtermal Analysis (DTATGA) TGADTA thermo-gram (Figure 6) shows that the breakdown of Gh-B is doneon three exothermic steps and one endothermic step

315

280

245

210

175

140

105

70

35

000 13 26

Lsec 300 0 Cnts 0000keV Det octane plus det39 52 65 78 91 104 117 130

Figure 4 SEM images and EDX analysis of Gh-B

Table 2 Chemical elements of Gh-B and their

Element O Fe Mg Al Si S K Ca masses 479 4 138 1 238 07 06 82

Journal of Chemistry 5

(i) First degradation step with loss of mass on theorder of 12 due to the removal of water moleculesinfirm bound or adsorbed on external faces of thecrystals )is step manifests itself by two distinctendothermic peaks on curve ATD at two tem-peratures 7070degC and 12895degC respectively

(ii) Second loss of almost 895 mass at 67937degC(ATD) which is manifested by wide and asym-metric peak corresponding to decomposition of theearly mixed carbon of magnesia and the calcium

(iii) Exothermic pic around 528degC corresponding toallotropic transformation of the stevensite inenstatite

)at transformation of stevensite in enstatite is repre-sented by the following equation

2Mg3Si4O10(OH)2 middot nH2O⟶ 3 MgSiO3 + MgO( 1113857 + 5SiO2

+ 2(n + 1)H2O

(10)

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

0 200 400 600 800 1000 1200 1400ndash0002

00000002000400060008001000120014

dVd

D (c

m3 g

A)

Pore diameter (Adeg)

D = 72812A

Vol

ume a

dsor

bed

(cm

3 g S

TP)

Relative pressure (PP0)

Adsorption Desorption

Figure 5 N2 adsorptiondesorption isotherms of Gh-B

0 100 200 300 400 500 600 700 80050

55

60

65

70

75

80

85

90

95

100

Temperature (degC)

Wei

ght (

)

12412615mg

89521886mg

11925degC

7070degC

52848degC

67937degC

ATGATD

ndash0213

ndash0142

ndash0071

0000

0071

0142

0213

Tem

pera

ture

diff

eren

ce (deg

Cm

g)

Figure 6 DTA and TGA plots of Gh-B

6 Journal of Chemistry

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

observed at 880 cmminus1 )e bands which appear around 1021684 and 463 cmminus1 are attributed to the vibrations of the SiO2group (Figure 3)

314 SEMEDX and BET Analysis SEMmicrograph of Gh-B (Figure 4) shows that the morphology of the Gh-B is closeto hectorite and the particles from different sizes have theappearance of sheets which oriented parallel to each other asindicated by Caillere and Henin [22]

)e chemical elements contained in natural clay (Gh-B) were detected by EDX analysis and the results showthat Gh-B has a higher percentage of silica (Table 2)mainly due to the presence of majority of quartz followedby magnesia )ese results are in agreement with XRD andXRF analysis

Table 2 gives the chemical elements and their masspercentages determined by the EDX analysis

)e nitrogen adsorptiondesorption isotherms of Gh-Bshow that according the IUPAC classification isothermobtained is type IV characteristic of solid mesoporous withonset the hysteresis of H3 type After calculating using theBET method the specific surface is 296m2g

)e pore size distribution is determined from desorptionisotherm by the BJH method shown in Figure 5 )is lattershows that the pore diameter is in the order of 73 A and thusconfirms the mesoporosity of the structure of the Gh-B

315 gtermal Analysis (DTATGA) TGADTA thermo-gram (Figure 6) shows that the breakdown of Gh-B is doneon three exothermic steps and one endothermic step

315

280

245

210

175

140

105

70

35

000 13 26

Lsec 300 0 Cnts 0000keV Det octane plus det39 52 65 78 91 104 117 130

Figure 4 SEM images and EDX analysis of Gh-B

Table 2 Chemical elements of Gh-B and their

Element O Fe Mg Al Si S K Ca masses 479 4 138 1 238 07 06 82

Journal of Chemistry 5

(i) First degradation step with loss of mass on theorder of 12 due to the removal of water moleculesinfirm bound or adsorbed on external faces of thecrystals )is step manifests itself by two distinctendothermic peaks on curve ATD at two tem-peratures 7070degC and 12895degC respectively

(ii) Second loss of almost 895 mass at 67937degC(ATD) which is manifested by wide and asym-metric peak corresponding to decomposition of theearly mixed carbon of magnesia and the calcium

(iii) Exothermic pic around 528degC corresponding toallotropic transformation of the stevensite inenstatite

)at transformation of stevensite in enstatite is repre-sented by the following equation

2Mg3Si4O10(OH)2 middot nH2O⟶ 3 MgSiO3 + MgO( 1113857 + 5SiO2

+ 2(n + 1)H2O

(10)

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

0 200 400 600 800 1000 1200 1400ndash0002

00000002000400060008001000120014

dVd

D (c

m3 g

A)

Pore diameter (Adeg)

D = 72812A

Vol

ume a

dsor

bed

(cm

3 g S

TP)

Relative pressure (PP0)

Adsorption Desorption

Figure 5 N2 adsorptiondesorption isotherms of Gh-B

0 100 200 300 400 500 600 700 80050

55

60

65

70

75

80

85

90

95

100

Temperature (degC)

Wei

ght (

)

12412615mg

89521886mg

11925degC

7070degC

52848degC

67937degC

ATGATD

ndash0213

ndash0142

ndash0071

0000

0071

0142

0213

Tem

pera

ture

diff

eren

ce (deg

Cm

g)

Figure 6 DTA and TGA plots of Gh-B

6 Journal of Chemistry

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

(i) First degradation step with loss of mass on theorder of 12 due to the removal of water moleculesinfirm bound or adsorbed on external faces of thecrystals )is step manifests itself by two distinctendothermic peaks on curve ATD at two tem-peratures 7070degC and 12895degC respectively

(ii) Second loss of almost 895 mass at 67937degC(ATD) which is manifested by wide and asym-metric peak corresponding to decomposition of theearly mixed carbon of magnesia and the calcium

(iii) Exothermic pic around 528degC corresponding toallotropic transformation of the stevensite inenstatite

)at transformation of stevensite in enstatite is repre-sented by the following equation

2Mg3Si4O10(OH)2 middot nH2O⟶ 3 MgSiO3 + MgO( 1113857 + 5SiO2

+ 2(n + 1)H2O

(10)

00 02 04 06 08 100

50

100

150

200

250

300

350

400

450

0 200 400 600 800 1000 1200 1400ndash0002

00000002000400060008001000120014

dVd

D (c

m3 g

A)

Pore diameter (Adeg)

D = 72812A

Vol

ume a

dsor

bed

(cm

3 g S

TP)

Relative pressure (PP0)

Adsorption Desorption

Figure 5 N2 adsorptiondesorption isotherms of Gh-B

0 100 200 300 400 500 600 700 80050

55

60

65

70

75

80

85

90

95

100

Temperature (degC)

Wei

ght (

)

12412615mg

89521886mg

11925degC

7070degC

52848degC

67937degC

ATGATD

ndash0213

ndash0142

ndash0071

0000

0071

0142

0213

Tem

pera

ture

diff

eren

ce (deg

Cm

g)

Figure 6 DTA and TGA plots of Gh-B

6 Journal of Chemistry

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

32 Kinetics Adsorption Figure 7 demonstrates that thequantity of polyphenols adsorbed at different temperaturesis in the order 161mgg and considered important becauseof the high specific surface area (296m2middotgminus1) of Gh-B )ecurves demonstrate that the adsorption kinetics is very quickat the start due to the presence of the active sites at the startof adsorption and the equilibrium was established after 2 h(about 60min at 25degC) )e quantities of polyphenolsadsorbed onto Gh-B diminished from 161 to 123mgmiddotgminus1

when the temperature increases from 25degC to 45degC indi-cating that the temperature higher than 25degC destabilizes theforce of adsorption and also decreases the interaction be-tween Gh-B and polyphenols and therefore the adsorptionprocess is exothermic )e same observation was found byDe Chimie et al works of adsorption of polyphenols fromOMW by pomace olive which is utilized as an active carbon[23]

)e plots of ln (qeminusqt) and tqt according to time(equations (2) and (3) respectively) are obtained inFigures 8(a) and 8(b) respectively We can wind up thatpolyphenols are adsorbed onto Gh-B and excellently follow-up the PSO model (Figure 8(a)) )is is endorsed by theseadsorbed quantities determined theoretically (qth) and arevery near to those obtained experimentally (qexp) R2 099(Table 3)

In this study we notice that when the temperature of thesolution raises the apparent constant of the PSO speed K2increased probably due to chemisorption phenomena )esame observation has been obtained in the adsorption ofphenolic compounds from OMW on orange peel [24] onactive carbon [25ndash28] onto resin [29] on onion [30] inremoval of basic yellow cationic dye [21] and in methylviolet by the same adsorbent (ghassoul) [20]

321 IPD )e plot of the adsorbed quantity qt versus t12shows that polyphenols are adsorbed in two steps (Figure 9))e first one is quick this is due to the transfer of poly-phenols from OMW to the outside of the adsorbent )esecond step is typified by a slight evolution to equilibrium

and it represents interaction between ghassoul and poly-phenols )ese results validate an adsorption according to akinetic of the PSO However the values of constant C aredifferent to 0 (Table 4) that shows the rate of polyphenoladsorption onto Gh-B is not controlled only by IPD step)is results is an agreement with Valderrama et al and-Lavinia et al [31 32]

322 Study of Activation Energy Ea )e tracing of ln K2 asfunction to 1T allows to determine activation energy Eafrom the slope of the equation line Arrhenius Figure 10shows that the experimental points give a line when R2 isvery near to 1)e value of activation energy (90622 kJmol)given by the slope of the Arrhenius plot demonstrates thatthe adsorption of polyphenols from OMW can be controlledby a chemisorption phenomenon )is phenomenon isconfirmed by the obtained kinetic results )is is in ac-cordance with the works of M kessoum[33] in the inves-tigation of adsorbed polyphenols on a commercial activecarbon (Picachem 150) but it is in disagreement with theresults of Senol et al [28] in the kinetic studies of biophenoladsorption onto commercial activated carbon with differentparticle sizes and at varied temperature)ey have found thephysisorption phenomenon because the values of Ea areincluded between 2722 and 3376 kJmol

33 Adsorption Isotherms )e curves of nonlinear trans-forms obtained by Langmuir and Freundlich models areshown in Figure 11 and the different parameters deducedfrom the two models are grouped in Table 5

In Figure 11 it is clearly demonstrated that the adsorbedquantity of the polyphenols qmax increases when the initialpolyphenol concentration C0 grows until the saturationTable 5 shows a good linear correlation coefficient R2 close to1 for both isotherms Langmuir and Freundlich

However the values n from the Freundlich model forvarious temperatures (Table 5) are greater than 1 and thevalues of KF are large indicating that the adsorption isfavorable For the Langmuir model the values of RL are

0 50 100 150 2000

50

100

150

Qad

s (m

gg)

Time (min)

25degC35degC45degC

Figure 7 Various adsorption kinetic according to time of three temperatures

Journal of Chemistry 7

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

Table 4 Parameters of IPD

Step 1 Step 2T (degC) C Kd (gmiddotmgminus1middotminminus12) R2 C Kd (gmiddotmgminus1middotminminus12) R2

25 183 2514 099 10555 441 09735 276 2307 098 10806 210 09645 082 2295 099 12304 0032 053

0 50 100 150 200ndash4

ndash2

0

2

4

6

ln (q

e ndash qt)

t (min)

25degC35degC45degC

(a)

25degC35degC45degC

0 50 100 150 20000

05

10

15

tqt (

min

gm

g)

t (min)

(b)

Figure 8 Linear portrayal of kinetic model of polyphenols adsorption onto Gh-B for both models (a) PFO and (b) PSO

Table 3 PFO and PSO parameters

PFO model PSO modelT (degC) qads (exp) (mgg) K1 (minminus1) qads (theorique) (mgg) R2 qads (theorique) (mgg) K2 (g(gmiddotmin) R2

25 161 0049 171 0872 166113 0001 099935 134 0046 70 0920 135685 0003 099945 123 0024 8676 0083 124069 0010 0999

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

160

180

q ads

(mg

g)

q ads

(mg

g)

q ads

(mg

g)

t12 t12 t12

25degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

35degC

0 2 4 6 8 10 12 140

20

40

60

80

100

120

140

45degC

Figure 9 IPD plots for different temperatures

8 Journal of Chemistry

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

near to 1 in the concentration domain from 0 to 58 mgLbut the amount of adsorbed qmax calculated from thismodel is much different from those foundexperimentally

)erefore the two models are favorable to describe theadsorption phenomena of polyphenols onto ghassoul claybut Freundlich model is more suitable because the theo-retical amount of polyphenols (qmax) calculated from theLangmuir model is very far to the experimental value for alltemperatures )ese results are similar to those obtained byMounia et al and Jedi et al who worked on removing

phenolic compound by adsorption onto wheat bran andbentonite respectively [33 34]

331 gtermodynamic Parameters )e negative value ofΔH0 (minus014 kJmol) (Table 6) shows that the adsorption ofpolyphenols onto Gh-B is an exothermic process in ac-cordance with the kinetic studies (qmax decreases with theincrease in temperature) )e order of the process is indi-cated by the negative value of ΔS0 (minus4625 JKmiddotmol) )eadsorption process is spontaneous because of the negative

0 100 200 300 400

0

100

200

Experimental pointLangmuirFreundlich

45degC

0 100 200 300 400

0

100

200

35degC

0 100 200 300 400

0

100

200

q e (m

gg)

q e (m

gg)

q e (m

gg)

Ce (mgL) Ce (mgL) Ce (mgL)

25degC

Figure 11 Adsorption isotherm for polyphenols onto ghassoul clay

Table 5 Parameters of adsorption isotherms

Langmuir FreundlichT (degC) qmax (mgg) KL (mgg) RL R2 n KF (mgg) R2

25 41191 451times 10minus3 099 099 190 1180 09935 39778 340times10minus3 099 099 177 806 09845 26581 938times10minus3 099 099 296 2840 099

000315 000320 000325 000330 000335

ndash70

ndash65

ndash60

ndash55

ndash50

ndash45

ln (K

2)

1T (Kndash1)

Figure 10 Arrhenius slope for adsorption of polyphenols

Journal of Chemistry 9

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

value of Gibbs free energy )ese outcomes are identical toMakhlouf et al in the study of the adsorption of phenoliccompounds onto mesoporous material [35]

34 Analysis of theAdsorption by FTIR )e spectrum of Gh-B after adsorption in Figure 12 shows new bands of vi-bration A shouldering to 3472 cmminus1 and an intense band at3437 cmminus1 corresponding to hydroxyl stretching vibration offree and bonded minusOH groups of the polyphenols respec-tively We also noted the presence of new bands at 2922 cmminus1

and 2855 cmminus1 corresponding to aromatic C-H and otherbands at 1732 and 1385 cmminus1 attributed to the C-O group ofpolyphenols (Figure 12) )ese results indicate the presenceof polyphenols and confirmed that these compounds areadsorbed onto ghassoul

4 Conclusion

In this study we are interested in testing the effectiveness ofnatural clay ldquoGh-Brdquo in the elimination of polyphenols fromolive mill wastewater (OMW)

)e obtained results are as follows

(i) )e natural clay ghassoul is majority constituted ofsilica and magnesia )is result is in agreement withXRD XRF and SEMEDX

(ii) )e quantity of the polyphenols adsorbed at dif-ferent temperature has been of order 161mgg andit is considerably important because of high specificsurface area (296m2middotgminus1) of Gh-B

(iii) )e examination of the adsorption kinetic ofpolyphenols onto Gh-B demonstrates that adsorp-tion is done in two steps )e initial step is fast andthe balance comes at 2 h of contact )e next step is

typified by slow evolution to equilibrium and ad-sorption kinetic realized at pseudo-second-order(PSO) model

(iv) )e experimental isotherms are preferentially de-scribed by the Freundlich model and the thermo-dynamic study indicates that the adsorption ofpolyphenols was exothermic in nature ΔH0lt 0ordered ΔS0lt 0 and spontaneous ΔG0lt 0

(v) All outcomes demonstrated that ghassoul was aneffective and feeble cost adsorbent for the elimi-nation of polyphenols from ldquoOMWrdquo

Data Availability

)e authors affirm that all information fundamental to thediscoveries of this examination are completely accessiblewithout limitation

Conflicts of Interest

)e authors declare that there are no conflicts of interest

Acknowledgments

)is work was done in the frame work of the project (PPR2)supported by Ministry of National Education ProfessionalTraining Higher Education and Scientific Research Mo-rocco (MENFPESRS) and National Center for Scientific andTechnical ResearchRabat Morocco (CNRST)

References

[1] B Zghari F Benyoucef and A Boukir ldquoImpact environ-nemental des margines sur les eaux drsquooued oussefrou car-acterisation physico-chimique et evaluation parchromatographie gazeuse couplee a la spectrometrie de masse( CPG-SM ) the environmental impact of olive mill waste-water in oussefrourdquo American Journal of Innovative Researchand Applied Sciences vol 2429ndash5396 pp 276ndash291 2018

[2] A L I Agoumi and A Debbarh Ressources en eau et bassinsversants du Maroc 50 ans de developpement Report preparedwithin the framework of the ldquoWater Management of scarcityrdquoorganized by the Association of Moroccan Engineers ofBridges and Roads pp 13ndash62 Marocco 2005

[3] B Ibrahimoglu and M Z Yilmazoglu ldquoDisposal of olive millwastewater with DC arc plasma methodrdquo Journal of Envi-ronmental Management vol 217 pp 727ndash734 2018

[4] S Dermeche M Nadour C Larroche F Moulti-mati andP Michaud ldquoOlive mill waste biochemical characterizationand valorization strategiesrdquo Process Biochemistry vol 48no 10 pp 1532ndash1552 2013

[5] U Tezcan Un S Uǧur A S Koparal and U BakirOǧutveren ldquoElectrocoagulation of olive mill wastewatersrdquoSeparation and Purification Technology vol 52 no 1pp 136ndash141 2006

[6] T Chatzistathis and T Koutsos ldquoOlive mill wastewater as asource of organic matter water and nutrients for restorationof degraded soils and for crops managed with sustainablesystemsrdquo Agricultural Water Management vol 190 pp 55ndash64 2016

[7] C H Neoh Z Z Noor N S A Mutamim and C K LimldquoGreen technology in wastewater treatment technologies

Table 6 )ermodynamic parameters of adsorption of polyphenolsonto Gh-B

T (K) ΔG0 (kJmol) ΔS0 (JKmiddotmol) ΔH0 (kJmol) R2

298 minus311minus4625 minus014 099308 minus118

318 minus022

4000 3500 3000 2500 2000 1500 1000 500

Abs

orba

nce (

au)

Wavenumber (cmndash1)

After adsorptionGh-B

3437

2922

1021

880684

4633472

28551732

14501641

1385

Figure 12 FTIR spectra of Gh-B before and after adsorption

10 Journal of Chemistry

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11

integration of membrane bioreactor with various wastewatertreatment systemsrdquo Chemical Engineering Journal vol 283pp 582ndash594 2016

[8] T Coskun E Debik and N M Demir ldquoTreatment of olivemill wastewaters by nanofiltration and reverse osmosismembranesrdquo Desalination vol 259 no 1ndash3 pp 65ndash70 2010

[9] D V K Curi and S G Velioglu ldquoTreatment of olive oilproduction wastes treatment and disposal of liquid and solidindustrial wastesrdquo in Proceedings of thegtird Turkish-GermanEnvironmental Engineering Symposium pp 189ndash205 Istan-bul Turkey June 1979

[10] M O J Azzam ldquoOlive mills wastewater treatment usingmixed adsorbents of volcanic tuff natural clay and charcoalrdquoJournal of Environmental Chemical Engineering vol 6 no 2pp 2126ndash2136 2018

[11] V L Singleton R Orthofer and R M Lamuela-Raventosldquo[14] Analysis of total phenols and other oxidation substratesand antioxidants by means of folin-ciocalteu reagentrdquo inOxidants and Antioxidants Part A vol 299 pp 152ndash178Elsevier Amsterdam Netherlands 1999

[12] J Huang Y Zhou K Huang S Liu Q Luo and M XuldquoAdsorption behavior thermodynamics and mechanism ofphenol on polymeric adsorbents with amide group in cy-clohexanerdquo Journal of Colloid and Interface Science vol 316no 1 pp 10ndash18 2007

[13] H Yuh-Shan ldquoCitation review of lagergren kinetic rateequation on adsorption reactionsrdquo Scientometrics vol 59no 1 pp 171ndash177 2004

[14] Y S Ho and G McKay ldquoPseudo-second order model forsorption processesrdquo Process Biochemistry vol 34 no 5pp 451ndash465 1999

[15] T W Weber and R K Chakravorti ldquoPore and solid diffusionmodels for fixed-bed adsorbersrdquoAIChE Journal vol 20 no 2pp 228ndash238 1974

[16] S Muralidharan K Srikrishna and S Subramanian ldquoOpti-mized power generation using dynamic programmingrdquo In-ternational Energy Journal vol 8 pp 217ndash224 2007

[17] K R Hall L C Eagleton A Acrivos and T VermeulenldquoPore- and solid-diffusion kinetics in fixed-bed adsorptionunder constant-pattern conditionsrdquo Industrial amp EngineeringChemistry Fundamentals vol 5 no 2 pp 212ndash223 1966

[18] Y S Ho and G McKay ldquoSorption of dye from aqueoussolution by peatrdquo Chemical Engineering Journal vol 70 no 2pp 1227ndash1231 1999

[19] Y Seki and K Yurdakoccedil ldquoEquilibrium kinetics and ther-modynamic aspects of promethazine hydrochloride sorptionby iron rich smectiterdquo Colloids and Surfaces A Physico-chemical and Engineering Aspects vol 340 no 1ndash3pp 143ndash148 2009

[20] K Elass A Laachach A Alaoui andMAzzi ldquoRemoval ofmethylviolet from aqueous solution using a stevensite-rich clay fromMoroccordquo Applied Clay Science vol 54 no 1 pp 90ndash96 2011

[21] M Ajbary A Santos V Morales-florez and L EsquiviasldquoRemoval of basic yellow cationic dye by an aqueous dis-persion of Moroccan stevensiterdquo Applied Clay Sciencesvol 80-81 pp 46ndash51 2016

[22] R M S Caillere and S Henin Mineralogie des argiles 2Classification et omenclature Masson Paris France 1982

[23] R R De Chimie M Ziati F Khemmari and F DidoucheldquoRemoval of polyphenols from olive mill wastewater by ad-sorption on activated carbon prepared from peach stonesrdquoRevue Roumaine de Chimie vol 62 no 11 pp 865ndash874 2017

[24] H Wazani ldquoEtude de traitement de margine par adsorptionrdquopp 56-57 Faculte des Sciences Dhar lmahraz Fes Marocco2017 Master

[25] V Fierro V Torne-Fernandez D Montane and A CelzardldquoAdsorption of phenol onto activated carbons having dif-ferent textural and surface propertiesrdquo Microporous andMesoporous Materials vol 111 no 1ndash3 pp 276ndash284 2008

[26] M Abdelkreem ldquoAdsorption of phenol from industrialwastewater using olive mill wasterdquo APCBEE Procedia vol 5pp 349ndash357 2013

[27] A Kumar S Kumar and S Kumar ldquoAdsorption of resorcinoland catechol on granular activated carbon equilibrium andkineticsrdquo Carbon vol 41 no 15 pp 3015ndash3025 2013

[28] A Senol IM Hasdemir B Hasdemir and I Kurda ldquoAd-sorptive removal of biophenols from olive mill wastewaters(OMW) by activated carbon mass transfer equilibrium andkinetic studiesrdquo Asia-Pacific Journal of Chemical Engineeringvol 12 no 1 2017

[29] E Ferrer-polonio J A Mendoza-roca A Iborra-clar andL Pastor-alcantildeiz ldquoAdsorption of raw and treated by mem-branes fermentation brines from table olives processing forphenolic compounds separation recoveryrdquo Journal Chem-icalTechnology and Biotechnology vol 91 no 7 2016

[30] S Kuhn H RWollseifen R Galensa N Schulze-kaysers andB Kunz ldquoAdsorption of fl avonols from onion (Allium cepa L)processing residues on a macroporous acrylic resinrdquo FoodResearch International vol 65 2014

[31] C Valderrama J Barios M Caetano A Farran andJ Cortina ldquoKinetic evaluation of phenolaniline mixturesadsorption from aqueous solutions onto activated carbon andhypercrosslinked polymeric resin (MN200)rdquo Reactive andFunctional Polymers vol 70 pp 142ndash150 2010

[32] L Luvinia L Cocheci R Pode and I Hulka ldquoPhenol ad-sorption using Aliquat 336 functionalized Zn-Al layereddouble hydroxiderdquo Separation and Purification Technologyvol 196 pp 82ndash95 2018

[33] M Kessoum V Caqueret O Chedeville B CagnonS Bostyn and C Porte ldquoEtude de la cinetique et de lathermodynamique drsquoadsorption de composes phenoliques enmonosolutes et en melange sur charbon actifrdquo pp 26ndash282014

[34] A Mounia A Hafidi L Mandi and N Ouazzani ldquoRemovalof phenolic compounds from olive mill wastewater by ad-sorption onto wheat branrdquo Desalination and Water Treat-ment vol 52 no 13 pp 1ndash11 2015

[35] M Makhlouf R Hamacha F Villieras and A BengueddachldquoKinetics and thermodynamics adsorption of phenoliccompounds on organic-inorganic hybrid mesoporous mate-rialrdquo International Journal of Innovation and Applied Studiesvol 3 no 4 pp 1116ndash1124 2013

Journal of Chemistry 11